Bicyclic compound containing a diphenylamine nucleus



Patented June 10, 1947 BIGYGLIQ COMPOUND? GQNTAINING. A DIPH-ENYLAMINE N IZTGLEUSJ James G'..McNally" and J osephB. Dickey; Rochester; N. Y"., assignors to Eastman Kodak Com- Rochester, N. 2 a' corporation of New No Drawing. Application. Septemben 2,,1943,

Serial No. 500,998

7 Claims. I

This: invention relates tobicyclic compounds containing adiphenylamine nucleus. and more particularly: to: such compounds attached; to; the: same bcnzenenucl'eusofiW1 1i is only onernituo; group; said-n-itro'gmcupbeingin the ortholpositiom to the diphe-nylamine nitrogenlatomr, andra gnoup: selected from: the group consisting of alsultonsamide group: a sulf-onamidogroupin which a hy drogenatom hasbeen replaced by an: alcohol rad-is cal and a sulfonamido group in which one hydro gen. atom has beenreplaced by an amino group.

Compounds containing adiphenylamine nucleus in which there are two nitro groups attached to the same benzene nucleus, the nitro groups being int-hesortho positions to the diphenyiacnine nitrogen atom and-containingonthe same benzene nucleus a phenyl substituted sulfonami'de groupin the para position, to the diphenylamine nitrogenatom have been describcdby Ull'mannin Anna. 1;, vol..36fi,. page 1077? (19.09). These. prior diphenylamine compounds, We haue found, will dye textile materials comprising organic derivatives: of'cellulose; such as cellulosevacetatea How-- ever, the dyeingrspeedtis very low and the dyed textile materialis not resistant to fadinginllight.

Wehave now found new diphenyl-amine com pounds whichdifler fromtheprior compounds in containing but'one nitro group and in containing on the same benzene nucleus that contains the nitro'. eroup,.a.su1ronamido; group; alsulfonamido roup in which. a hydrogen atom has been re-' pl'acedi'by an alcoholradicaLinstead"of a phenyl radical, e,.,g:,. phenyl, or a; sultonamido. group in" whi'chone hydrogen atom is replaced. by an amino" group (-i.. e., .a sulfonhydrazido group); Our new' compounds. contrary to the action of the prior: compounds dye organic derivatives of cellulose. such as cellulose acetate, at a relatively rapi'dqrate and are relatively very stable to light.

a It is; accordingly, an. object; or, our inventionto; provide new diphenulamine compounds. A further object is to provide a process for preparing such compounds. A-still furthercbject is to provide materials dyed with such new compounds. Other objects willbecome apparent hereinafter. In accordance with our invention, We prepare our new: diphenylamine-compouhds. by condensing, in

the presence-of antacid-binding. agent,, a monocycliclprimary aromatic, amine otthe. benzene sericsewith, amonocyclic compound containing a. benzenenucleus and. containing on the benzene nucleus a-halogenatom and. only onet ni-tro group, said nitro group being.- in ortho position to, the

(or. zoo-3971c).-

2 halogen atom, said compound also containing 011 the b'enzene nucleus; inipara position. to the halogen atom a grouprselected. from the group consisting of a sulfonamido group and a sulfonamido group in which a; hydrogen atom has been replaced by an alcohol radical Exemplary of the monocyclic primary aromatic amines of the benzene series are aniline, o-anisidine, o-nitroaniline,

m-nitroanilinie; pa-nitroanilinm, o.-nitro-p-methoxyarnl'ine, o-am-inophenoh m-amni'ophenor paminophenol; ma-aminophenoxy' acetic. acid, 0-- aminophenoxy acid amide, p- (o-hydronyethom 5 aniline, o-(pesulfatoethoxy)-aniline, o-aminoacetophenone, m-aminoacetophenone, o-ni'tro-p-= chloroaniline, o-nitro-p-fluoroaniline, N-acetyl- N-(fi-hydroxyethyl) o -phenylenediamine and N,N-dimethyl-p-phenylerrediamine.

As monocyclic compounds containing a halogen atom, a nitro grouplan'd a sulfonamido group, the more readily available chlorine. compounds. are advantageouslyemployedt These compoundslmaycontain substituents onthe benzene. ring other. than the nitro and sultonanndogroups. However, in no case do the compounds contain more than onenitro group: 'Gneor both 025- the hyd rogen atoms of the sulformmi'degroup may be replaced by alcohol radicals,. e. g., methyl, ethyl, isoamyl, p-hydroxyethyl iil-methoxyethyl, allyl, benzyl, tetrahydroiurfnryl, cyclohexylg' 3-hydroxy- ,B-ethoxyethyl, cetyl, lauryl, ,B-sulfoethyl or ,c-sulfatoethyl. As acid-binding agents, the alkali metal carbonates are advantageously employed. Alkaline" earth. bicarbonates; alkali metal bicarbonates, alkaline earth carbonates; tertiary amines, or other acid-binding agents can be employed'.

Advantageously the monocyclic aromaticprimary amine isremployed in excess (about 1=.l; mole for each mole of halogenvcontaining. nitrobenzenesulfonamide). The excess-amine can heremoved after thecondensation by, steam distillation, or where the amineisnotmeadily steam distillable, it can be dissolved in dilute acid, e. g., 1 to 5 per cent aqueous hydrochloric or sulfuric acid, and therdye filtered 15mm the resulting solution. Where thea-mine is neithersteam distillable nor soluble in dilute acids, the dye is advantageously separated. from the excess amine by extraction with a. suitable solvent; are all yellow. incol'or.

The. following examples will" serve". to: illustrate our new dyes, and the. manner of obtaining the same.

Our new dyes 3 Example 1.-2-nitr0-4-suljonamidodiphenylamine In a flask, fitted with a mechanical stirrer, were placed 92.4 g. (1.1 moles) of sodium carbonate and 102.3 g. (1.1 moles) of aniline. The stirrer was started and the mixture in the flask heated to 125 C. To the hot mixture were added portionwise 236 g. (1 mole) of 4-chloro-3- nitrobenzene sulfonamide, so that the reaction does not become too vigorous. After the addition, heating was continued for 6 hours at 125 to 135 C; The reaction mixture was permitted to cool and then was steam distilled to remove unreacted aniline. The yellow dye remaining with the aqueous still liquors was filtered off, washed with water and dried in the air. It melted at 178 to 180 0.

Example 2.-2-nitro-4-sulfonamido-4'-methyldiphenylamine n CHONQSOzNH:

Example 3.-2-nitro-4-sulfonamid0-4'-ethomydiphenylamine This dye was prepared exactly as in Example 1, using 150.8 g. (1.1 moles) of p-phenetidine instead of 102.3 g. of aniline. The yellow orange dye melted at 161 to 163 C.

Exampl 4.2-nitro-4-sulfonamido-4'-ch.lorodiphenylamine Example 5.-2-nitro-4-suljonamidio-4-hydroxydiphenylamine i HOONQ-SWNH:

SOQNHZ This dye was prepared exactly as in Example 1, except that 120 g. (1.1 moles) of p-aminophenol were employed instead of 102.3 g. of aniline, and instead of steam distilling, the excess p-aminophenol was dissolved by adding 3 per cent sulfuric acid to the reaction mixture. The

yellow dye was filtered from the resulting aqueous solution, washed with water and dried in the air. It melted at 228 to 230 C.

Example 6.-2-nitro-4-sulj0namido-2'-ethoa:ydiphlenylamine This dye was prepared exactly as in Example 1, using 150.8 g. (1.1 moles) of o-phenetidine instead of 102.3 g. of aniline. The yellow dye melted at 171 to 172 C.

Example 7.--2-nitro-4-sulfonamido- 4' -methylacetaminodiphenylamine This dye was prepared exactly as in Example 1, except that 180 g. (1.1 moles) of N-methyl-N- acetyl-p-phenylenediamine were used instead of 102.3 g. of aniline, and instead of steam distilling, the excess N-methyl-N-acetyl-p-phenylenediamine was dissolved by adding 3 per cent sulfuric acid to the reaction mixture. The yellow dye was filtered from the resulting solution, washed with water and dried in the air. It melted at 245 to 249 C.

Example 8.-2-nitro-4-sulfonamido 4 cyanomethyldiphenylamine NO-CHTONOSOZNH:

This dye was prepared exactly as in Example 1, except that g. (1.1 moles) of p-aminophenylacetonitrile were employed instead of 102.3 g. of aniline. The yellow dye melted at 245 to 250 C.

Example 9.--2-nitro-4-sulfonamid0-4-(p-phenylazophenyl) -diphenylamine Example 10.-2-nitro 4 sulfonethylamido 4' methomydiphenylamz'ne i omoONQsozNHom This dye was prepared exactly as in Example 1, except that 135.3 g. (1.1 moles) of p-anisidine were employed instead of 102.3 g. of aniline, and 264 g. (1 mole) of 4-chloro-3-nitrobenzenesulfonethylamide were employed instead of 236 g. of 4-chloro-B-nitrobenzenesulfonamide. The yellow dye melted at 122 to 124 C.

ample 11.-2-nitro desdlfmiditnthyidmidoq?- methyldiphenylamine Example 12.2 nitro-4-sulfonmethozcyethylamido-4'-eth0xydiphenylamine This dye was prepared exactly as in Example 1, except that 150.8 g. (1.1 moles) of p-phenetidine were employed instead of102 3'g: of aniline, and 294 .g. (1' mole) of 4-ch1oro-3-nitrobenzenesulfonmethoxyethylamide were employed instead of 236 g. of 4-ch1oro-3-nitrobenzenesulfonamide. The yellow dyemelted at 137 to 140* C.

Example 13.2-nitro-4-suZjon-p-hydromyethylamide-4'-eth0xydiphenylamine Thisdye was preparedexacfly as in Example 1, except that 150.8 g. 1.1 moles) of p-phenetidine were'employed instead of 102.21g. of aniline; and 280 g. (1 mole) of 4-ch1oro-3-nitrobenzene-fl hydroxyethylsulfonamide were employed instead of 236 g; of4 ch1oro-3 nitrobenzenesulfonamide.

The'yellow dye meltedat 165to1fi7 GH2-CH1 oeNnom-on' em This dye was prepared exactly as in Example 1, except that 320 g. (1 mole) of 4-ch10r0-3-nitrob e n z e n e sulfontetrahydrofurflirylsulfonamide were employed instead of 236 g. of4-chloro-3- nitrobenzenesulfonamide. The .yellow dye melted at 101 to 104 C. i

In a manner similar to that illustratedin the on one part of the;

- temperature: waskept' at310 to 20-- The. QchioroJ which precipitated was: filtered off,, washed with 6 dboveiexamplesithetollowing additional diphenylamineteumpounds were prepared.

The 4-ch-loro-3mitrobenzenesulfonamidei em? ployed in some of the examples: above was prepared by; themethod of B. Fischer (Ber-z 24, 3190) by condensing; 4-ch1oro-3 mitrobenzene sulionirl chloride. with: ammonium: carbonate, or better by adding- 2.5 moles, of dilute ammonium; hydroxide toiaw slurry of one; 111018101: tchlozro-iirnitzzoben zone: suifonylchloride. The=-su1fonamide; melts; at 2510935. C; andsboilsa-t 175 to 176*- C. amitmbenzeneisul-ionyl: chloride was preparediby condens n rsodium- 4-chloro-3-nitrobenaena sulfonate -Mth phosphorous: pentaehloride (R. Fisteher;, Ber; 24 31- onby the actiom 01 3i puts wweight 'otineshly sodium salt oi 4-ch1oror-3rnitrobenzene' sulfonic acid at 150 C. for several hours; 4-chloro-3-nitrobenzene sulfonylchloride melts'at" 61 to 62% @uuneor. 4' ehI0roF3-nitmbenzene su-lilonier acid was: prepared; by: sulfon ating o cliloronitrobenzene with: fuming: sulfuric acid according to the methodpf' P; Fisehen- -(-B 24,

dp-chloro iie-nitrobenzene suliionamides in which one orboththydrogematoms 01 the sulfonamide groupzlaizes replaced: by alcohol; radicals were prepared? by condensing4,-chloro-3-nitrobenzene sulfsmyli ohloridewith amines; Toipreparer ls-chloro- 3:-'nitrobenzene sulfonmethylamide, one: mole of "b-chioro-3-nitrobenzene sulfonyi chloride: was dissolyediiim 500 COL. of acetone, andtol this solution were? added; with; stirring, two moles: of methy1wamine0 per cent water solution); ll'he 01' during the entirer'eaetion. One-ghoul after the; addition of the methyl amine was completed, Volumes of :cold: water: were added to the reaction mixture. -ni'trobenzenesulIon-methylami'de water and dried; in the air. It melted at 61 to 1 63 C; In amexaetly similarmanner, the followinguwere: prepared: using the appropriate amine inqeaclr case:

Sulfonamide M. P

4=chl ro-3-nitr0benzene di rhethyl 99-100 4-ehlono-3mi-trobenzene isopropy M 73:75 4-chloro 3 nitrobenzene tetrahydrofurfu 75-77 el-chloro-B-nitrobenzene fi-methoxyethyl 31-83 4 -ohloro-3vliitrobenzene ethyhH, .v 97400 let-ehlonorspitrphenzene fi hydrox ethyl. -117 4-chloro-3-nitrebenzene butyl Mi--. ----1 6041 distilled: ehlorosulfionie; acid 'ters, such as cellulose however, the use of a The ,4. chloro'.3-nitrobenzenesulfonhydrazide was prepared by adding 4-chloro-3-nitrobenzene sulfonyl chloride to a slight excess of hydrazine in water solution. It melted at 136 to 137 C.

The new diphenylamine compounds of our invention are of greatest utility for the coloration ot-textile materials comprising organic derivatives of cellulose. for the coloration of non-vegetable textile fibers,

ored. The coloration produced by the diphenylamine compounds of our invention is yellow.

Typical organic derivatives of cellulose that can be colored include the hydrolyzed, as Well as the unhydrolyzed, cellulose carboxylic esters,

such as cellulose acetate, cellulose propionate and cellulose butyrate, and the hydrolyzed, as well as the unhydrolyzed mixed cellulose carboxylic esacetate propionate and cellulose acetate butyrate, and the cellulose others such as methyl cellulose, ethyl cellulose and benzyl cellulose. I

' The diphenylamine compounds of our invention are, for the most part, relatively insoluble in water and, accordingly, they may be advantageously directly" applied to the textile material undergoing coloration in the form of an aqueous suspension which can be prepared by grinding the dye to a paste, in the presence of a sulfonated oil, soap, or other suitable dispersing agent and dispersing the resulting paste in water. In some instances, the compounds may possess sufficient solubility in'water to render the use of a dispersing agent unnecessary. Generally speaking,

dispersing agent is desirable. 7

Direct dyeing operations can, with advantage, be conducted at temperatures ofabout 75 to 85 C., but any suitable temperature may be used. Thus, the textile material to be dyed or colored is ordinarily added to the dye bath at a temperature lower than that at which the main portion of the dyeing is to be effected, a temperature of from 45 to 55 C., for example, following which the temperature is raised to that selected for carrying" out the operation. The temperatur at which the dyeing operationis continued may vary somewhat depending upon the particular material undergoing coloration. As is understood by those skilled in the art, the intensity of dyeing can be varied by varying the proportion or dye to the material undergoing coloration. Generally speaking, 1 to 3% by weight of dye to material is employed, although any desired proportions canbe used.

Suitable dispersing agents are disclosed in our United States Patent 2,115,030, issued April 26, 1938. The process disclosed in this patent for the dyeing of cellulose acetate can be used in applying the dyes of the present invention to cellulose acetate. While a satisfactory method for dyeing has been disclosed herein, it will be understood that any other suitable methods for dyeing the non-vegetable textile materials named herein can be employed. Lacquers may be colored with the dye compounds of our invention by the methods customarily employed in the lacquer art.

The term nylon is intended to describe a linear polyamide resin, such as set forth in United States Patent 2,071,250, dated February 16, 1937.

The term sulfonamido is intended to mean a group of the following formula:

The term alcohol radical is intended to mean any radical derivable from an alcohol by dropping the OH group, e. g., ethyl from ethyl alcohol, benzyl from benzyl alcohol, allyl from allyl alcohol, tertiary butyl from tertiary butyl alcohol, etc.

.What We claim as our invention and desire to be secured by Letters Patent of the UnitedStates 1s: l. A yellow dye compound of the following general formula:

wherein R representsan alkyl group.

3. A yellow dye compound of the following formula: I

i N-OSO2NH2 4. A process for preparing a diphenylamine compound comprising condensing, in the presence of an acid-binding agent, a monocyclic primary aromatic amine of the benzene series with a monocyclic compound containing a benzene nucleus and containing on the benzene nucleus a halogen atom and only one nitro group, said nitro group being in ortho position to the halogen atom, said compound also containing on the benzene nucleus in para position to the halogen atom a CiHsO group wherein R1 represents a member selected ,from the group consisting of a hydrogen atom, an alkyl group, a hydroxyalkyl group and an alkoxyalkyl group.

5. A process for preparing a diphenylamine compound comprising condensing, in the presence of an alkali metal bicarbonate acid-binding agent, a monocyclic primary aromatic amine of the henzene series with a monocyclic compound containing a benzene nucleus and containing on the benzene nucleus a halogen atom and only one nitro group, said nitro group being in ortho position to the halogen atom, said compound also containing on the benzene nucleus in para position to the halogen atom a group wherein R1 represents a member selected from the group consistingv of a hydrogen atom,

an alkyl group, a hydroxyalkyl group and an alkoxyalkyl group.

6. A process for preparing a diphenylamine compound comprising condensing, in the presence of a sodium bicarbonate acid-binding agent, a monocyclic primary aromatic amine of the benzene series with a monocyclic compound containing a benzene nucleus and containing on the benzene nucleus a halogen atom and only one nitro group, said nitro group being in ortho position to the halogen atom, said compound also containing on the benzene nucleus in para position to the halogen atom a group wherein R1 represents a member selected from the group consisting of a, hydrogen atom, an alkyl group, a hydroxyalkyl group and an alkoxyalkyl group.

REFERENCES CITED The following references file of this patent:

UNITED STATES PATENTS are of record in the Number Name Date 1,709,292 Wagner Apr. 16, 1929 2,080,704 Fischer May 18, 1937 OTHER REFERENCES Northey, Chem. Reviews, vol. 27, No. 1, August 1940, page 140.

Fischer, Berichte Deut. Chem. Ges., vol. 24 (1 891), pages 3793-94 and 95.

Certificate of Correction Patent No. 2,422,029. June 10, 1947.

numbered patent requiring correction as follows: Column 3, line 60, Example 4, strike out in first occurrence, and insert instead with; column 4, lines 45 and 46, Example 9, for (p-phenylazophenyl) read phenylazo; same column, line 65, Example 10, for that portion of the formula reading -SO NHCH read -SO NH0 H column 5, line 17, Example 12, for sulfonmethoxyethylamidoread subon-fl-methozyethylamido same example, lines 28 and 29, for "nitrobenzenesulfonmethoxyethylamide" read nitrobenzenesub'omfl-methowyethylamide; same column, Example 15, line 71, for "sulfontetrahydrofurfurylsulfonamide read sulfantetrabydrofmjurylamide; column 6, he 42, for uncor read uncorrected; and that the said Letters Patent should be read with these corrections therein that the same may conform to the record of the case in the Patent Office.

THOMAS F. MURPHY,

Assistant Commissioner of Patents. 

